CN108656303A - The preparation method and applications method of thermosetting property water soluble phenol resin nano-powder adhesive - Google Patents
The preparation method and applications method of thermosetting property water soluble phenol resin nano-powder adhesive Download PDFInfo
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- CN108656303A CN108656303A CN201810485953.XA CN201810485953A CN108656303A CN 108656303 A CN108656303 A CN 108656303A CN 201810485953 A CN201810485953 A CN 201810485953A CN 108656303 A CN108656303 A CN 108656303A
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- thermosetting property
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- 239000000853 adhesive Substances 0.000 title claims abstract description 79
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 79
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 57
- 239000011858 nanopowder Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002023 wood Substances 0.000 claims abstract description 60
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 230000029058 respiratory gaseous exchange Effects 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000012216 screening Methods 0.000 claims abstract description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229920001342 Bakelite® Polymers 0.000 claims description 9
- 239000004637 bakelite Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000012792 lyophilization process Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 235000015110 jellies Nutrition 0.000 claims 1
- 239000008274 jelly Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 52
- 235000019256 formaldehyde Nutrition 0.000 abstract description 25
- 238000003825 pressing Methods 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005452 bending Methods 0.000 description 28
- 230000003068 static effect Effects 0.000 description 28
- 238000007731 hot pressing Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 21
- 238000009835 boiling Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 230000008961 swelling Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 12
- 210000002268 wool Anatomy 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000000994 depressogenic effect Effects 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000011094 fiberboard Substances 0.000 description 4
- 230000013011 mating Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000011093 chipboard Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000219000 Populus Species 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009688 liquid atomisation Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
- B27N1/0209—Methods, e.g. characterised by the composition of the agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27G—ACCESSORY MACHINES OR APPARATUS FOR WORKING WOOD OR SIMILAR MATERIALS; TOOLS FOR WORKING WOOD OR SIMILAR MATERIALS; SAFETY DEVICES FOR WOOD WORKING MACHINES OR TOOLS
- B27G11/00—Applying adhesives or glue to surfaces of wood to be joined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
- B27N3/12—Moulding of mats from fibres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The present invention provides a kind of preparation method of thermosetting property water soluble phenol resin nano-powder adhesive, includes the following steps：Step 1, thermosetting property water-soluble phenolic resin adhesive stick the vacuum concentration of agent；Step 2, thermosetting property water-soluble phenolic resin adhesive sticks agent and carries out vacuum freeze drying after concentration；Step 3, grinding and screening after vacuum freeze drying.Nano-powder adhesive prepared by this method is used to be applied to high-moisture percentage artificial board substrate with dry method resin application methods, the hot pre-pressing process of type of respiration produces wood-based plate, artificial board substrate's energy consumption for drying can be reduced, improve the curing rate of adhesive, wood-based plate bonding strength is improved, free phenol content and burst size of methanal are reduced.
Description
Technical field
The present invention relates to a kind of preparation method and applications sides of thermosetting property water soluble phenol resin nano-powder adhesive
Method belongs to wood-based plate manufacturing field.
Background technology
Phenolic resin, which sticks agent, has the good characteristics such as glue-joint strength is high, resistance to ability of endurance boiling water is strong, thermal stability is good.But it is water-soluble
Property phenolic resin stick agent the shortcomings of there are Storage period is short, and curing rate is slow, and there are free-phenol and burst size of methanal, in addition also deposit
Low defect is being required to being glued substrate moisture rate, is hampering its application in wood-based panel industry.
General spray drying is a kind of suspended particles processing technology, is that feed liquid atomization is become tiny mist using high pressure
It drips, and evaporates the process of solvent formation power-product rapidly in heated drying medium.The drying means can make liquid adhesive exist
Continue polycondensation in heating process, molecular weight is caused to increase, physicochemical properties change, while the powder surface after drying is hard
Knot leads to dry powder grinding and again dissolving difficulty, and then influences glue performance.
In order to obtain ideal bonding strength, phenolic resin has sternly the relative moisture content of artificial board substrate when sticking agent solidification
Lattice requirement, base material relative moisture content is generally between 6 ~ 8%, at most no more than 10%, in order to advise the control of substrate moisture rate
In fixed range, the drying for consuming a large amount of energy for artificial board substrate is needed.Wood-based plate is produced using high-moisture percentage base material,
To reducing base material energy consumption for drying, Wood-based Panel Production cost, great meaning are reduced.It is limited to when phenolic resin sticks agent solidification to base material
The requirement of moisture content realizes that the splicing of high-moisture percentage base material needs new technical measures.
Patent CN107325765A provides a kind of spray drying preparation of melamine-formaldehyde-urea adhesive
And Wood composite preparation method for material, it is dry after powder without nanosizing milled processed, when use, need to be dissolved in water, and base material contains
Water rate 8% hereinafter, using wet method resin application methods, conventional pre-pressing process.
Patent of invention CN104493948B provides a kind of preparation method of high-moisture percentage particieboard, and the moisture content of wood shavings is
20 ~ 40%, using liquid resin application methods, resin added is 5 ~ 8%, conventional pre-pressing process, and adhesive used is that blocked polyurethane is pre-
Adhesive is blended with melamine-urea formaldehyde in aggressiveness.
It is the method using electrostatic atomization that patent of invention CN103737695B, which provides a kind of dry method glue applying method, by dry powder
It is applied in high-moisture percentage wood shavings, fiber, the dry powder composition is extremely complex, is micron order, using conventional pre-pressing process.
Invention content
The present invention provides a kind of thermosetting property water-soluble phenolic to solve drawbacks described above and deficiency existing in the prior art
The preparation method and applications method of urea formaldehyde nano-powder adhesive, includes the following steps：
Step 1, thermosetting property water-soluble phenolic resin adhesive stick the vacuum concentration of agent；
Step 2 sticks agent to the thermosetting property water-soluble phenolic resin adhesive after step 1 concentration and carries out vacuum freeze drying；
Step 3 is ground and sieves to sticking agent through vacuum freeze drying treated thermosetting property water-soluble phenolic resin adhesive,
Obtain thermosetting property water soluble phenol resin nano-powder adhesive.
Wherein, in step 1, the vacuum concentration condition that thermosetting property water-soluble phenolic resin adhesive sticks agent is：Vacuum degree is 0.05
~ 0.09MPa, temperature concentrated in vacuo are 20 ~ 50 DEG C, and the solid content after concentration is 50 ~ 80%.
In step 2, vacuum freeze drying is divided into precooling process, lyophilization process and parsing drying process；Wherein,
The temperature of precooling process is less than -40 DEG C, and the vacuum degree of lyophilization process is 0.01 ~ 0.1mbar, freeze temperature is -40
~ -60 DEG C, the vacuum degree of parsing-desiccation process is 0.001 ~ 0.01mbar, freeze temperature -60 ~ -80 DEG C.
In step 3, grinding uses nanon ball-mill, and grinding temperature is between 190 ~ 280 DEG C；Particle diameter distribution model after screening
It is trapped among between 400 ~ 900nm.
The present invention also provides a kind of thermosetting property water soluble phenol resin nano-powder adhesives prepared using the above method
Application in Wood-based Panel Production, it is characterised in that include the following steps：
Step 1 is glued wood-based plate by the way of dry method sizing；
Step 2, artificial board substrate after sizing through mat formation or assembly after carry out the hot precompressed of type of respiration.
Further, sizing object is wood shavings layer, fibrous layer or veneer layer in artificial board substrate, the wood shavings layer, fibrous layer
And the relative moisture content of veneer layer is between 30 ~ 100%.
Further, in step 1, phenolic resin adhesive nano-powder is applied to wood shavings layer in such a way that air-flow blows and spreads
Or fiber layer surface, continuous mechanical agitation, resin added are the 5 ~ 20% of wood shavings layer or fibrous layer absolute dry weight；Or phenolic resin
Adhesive nano-powder is applied to the surface of veneer layer in such a way that air-flow blows and spreads, and resin added is 50 ~ 100g/m2。
Further, in step 2, the unit pressure of the hot precompressed of type of respiration is between 0 ~ 5MPa, and precompressed temperature is 190 ~ 250
Between DEG C, respiration rate is more than 3 times.
The advantageous effects that the present invention is reached：
A kind of preparation method of thermosetting property water soluble phenol resin nano-powder adhesive provided by the invention, vacuum freeze drying
It carries out at low temperature, especially suitable for thermal sensitivity, such as the drying of Thermosetting adhesive, molecular weight of material and physical chemistry after drying
Property is consistent with before drying, short texture, is in spongy, dissolves rapid and complete, property before meeting restores to freeze-drying at once after meeting water
Shape packs after the glutinous agent of phenolic resin is freeze-dried, and Storage period was up to 1 year or more.
Phenolic resin is prepared by hot lapping mode and sticks agent nano-powder, and the Mechanochemistry in high temperature and process of lapping can
Further to promote the volatilization of residual free formaldehyde and ether bond rupture in phenolic resin to release formaldehyde, residual free phenol is further
Volatilization.Bakelite resin nano powder application through high temperature and milled processed can significantly reduce free benzene when Wood-based Panel Production
Phenol content and burst size of methanal.
Using powder adhesive prepared by this method, nanometer grade powder has high specific surface area for nanoscale, is tool
The physical basis for having superpower adsorption effect, the phenolic resin adhesive nano-powder prepared using the method is from artificial board substrate
It adsorbs large quantity of moisture and dissolves rapidly and soak base material；Containing a large amount of not anti-in dissolved bakelite resin nano powder adhesive
The methylol answered, moisture and cellulose formation hydrogen bond with artificial board substrate, substantially increases bakelite resin nano powder glue
The Pre-pressure property of glutinous agent.
Dry method resin application methods are applied to high-moisture percentage artificial board substrate, and dry method is glued, and moisture-free in adhesive will not be led
Substrate moisture rate is caused to improve；And dissolving is needed to need to draw from base material to obtain wetability and mobility before adhesive solidification
Moisture, therefore base material must have higher relative moisture content, just contain when more than fibre saturated point, in base material and be easy to be inhaled
Attached Free water, thus artificial board substrate's unit only need it is dry to compared with high-moisture percentage or being not required to dry can be used to wood-based plate life
Production.Dry method is glued, and adhesive has 100% solid content, saves the moisture evaporation time in adhesive, and hardening time significantly shortens；
The solid content positive correlation of bonding strength and adhesive after powder dissolving remains to that the solid being glued far beyond wet method is kept to contain
Amount, bonding strength significantly improve.
Using hot prestressing technology, the moisture rapid vaporization in base material can be made, steam injection pressing effect is formed, be plasticized plate rapidly
Base reduces slab thickness；Promote the dissolving of nano-powder adhesive and precuring simultaneously, further increases Pre-pressure property.Using exhaling
Suction precompressed can promote formaldehyde newly-generated in still remaining free formaldehyde, procuring process after high temperature grinding with high pressure water
Discharge is forced in the exclusion of steam, further decreases the burst size of methanal of wood-based plate.
The present invention is glued by nano-powder adhesive dry method in high-moisture percentage base material, is given birth to using the hot pre-pressing process of type of respiration
Wood-based plate is produced, artificial board substrate's energy consumption for drying can be reduced, improves the curing rate of adhesive, improves wood-based plate bonding strength,
Reduce free phenol content and burst size of methanal.
Specific implementation mode
With reference to specific embodiment, the invention will be further described.Following embodiment is only used for clearly illustrating
Technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Patent of the present invention is further illustrated with reference to embodiment.
Embodiment 1
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.05MPa, the temperature control of adhesive when concentration
At 20 DEG C, it is concentrated into solid content 50%.Concentrate is in -40 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.01mbar, -40 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.001mbar, freeze temperature obtain dry powder at -80 DEG C.It is dry
Powder is ground through nanon ball-mill at 190 DEG C, is ground to screening value 400nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is applied in wood-fibred, and nano-powder is uniformly mixed with wood-fibred through mechanical agitation, and wood-fibred is dried to relative moisture content
30%, the applied amount of nano-powder is calculated with bone dry fiber quality 5%.Fiber sizing enters hot press precompressed, hot press after mating formation
190 DEG C are warming up to, heat preservation.The hot precompressed curve of slab is slowly to boost to unit pressure 5MPa, after pressurize 5min, slowly unloads and is depressed into
Unit pressure 0 MPa, pressurize 5min are denoted as breathing 1 time, thorough release after continuously breathing 3 times.Slab immediately enters separately after release
1 hot press hot pressing, 190 DEG C, hot pressing pressure 2MPa, hot pressing time 1min/mm of hot pressing temperature.Embodiment result：It is close in outdoor version
Spend fiberboard, density 0.75kg/m3, plate thickness 10mm, 0.85 MPa of internal bond strength, 37.2 MPa of static bending strength, elasticity modulus
2950 MPa, internal bond strength（Boiling experiment）0.33 MPa, thickness swelling rate 8.8%, burst size of methanal 2.4mg/
100g。
Comparative example：Using commercially available phenolic resin adhesive, wood-fibred relative moisture content is dried to 8%, resin added
Identical as implementation column 1, conventional precompressed mode, hot compression parameters are same as Example 1.Comparative example result：Density in outdoor version
Fiberboard, density 0.75kg/m3, plate thickness 10mm, 0.34 MPa of internal bond strength, 32.1 MPa of static bending strength, elasticity modulus
2750 MPa, internal bond strength（Boiling experiment）0.22MPa, thickness swelling rate 10.8%, burst size of methanal 3.7mg/
100g。
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, it is internal bond strength, quiet
Qu Qiangdu, elasticity modulus and internal bond strength（Boiling experiment）It is below in embodiment 1 and uses bakelite resin nano powder gluing
The wood-based plate that agent is produced；And thickness swelling rate and burst size of methanal are more than embodiment 1.
Embodiment 2
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.06MPa, the temperature control of adhesive when concentration
At 30 DEG C, it is concentrated into solid content 60%.Concentrate is in -45 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.02mbar, -45 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.002mbar, freeze temperature obtain dry powder at -70 DEG C.It is dry
Powder is ground through nanon ball-mill at 220 DEG C, is ground to screening value 500nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is applied in wood-fibred, and nano-powder is uniformly mixed with wood-fibred through mechanical agitation, and wood-fibred is dried to relative moisture content
100%, the applied amount of nano-powder is calculated with bone dry fiber quality 10%.Fiber sizing enters hot press precompressed, hot pressing after mating formation
Machine is warming up to 200 DEG C, heat preservation.The hot precompressed curve of slab is slowly to boost to unit pressure 4MPa, after pressurize 10min, is slowly unloaded
It is depressed into unit pressure 0.5 MPa, pressurize 5min, is denoted as breathing 1 time, thorough release after continuously breathing 10 times.Slab horse after release
It is upper to enter another 1 hot press hot pressing, 220 DEG C, hot pressing pressure 3.5MPa, hot pressing time 2.5min/mm of hot pressing temperature.Embodiment knot
Fruit：High wet type high density fiberboard, density 0.85kg/m3, plate thickness 8mm, 2.51 MPa of internal bond strength, static bending strength 68.2
MPa, 5750 MPa of elasticity modulus, 2.3 MPa of surface bonding intensity, thickness swelling rate 3.8%, burst size of methanal 2.1mg/
100g。
Comparative example：Using commercially available phenolic resin adhesive, wood-fibred relative moisture content is dried to 8%, resin added
Identical as implementation column 2, conventional precompressed mode, hot compression parameters are same as Example 2.Comparative example result：High wet type high density
Fiberboard, density 0.85kg/m3, plate thickness 8mm, 1.98 MPa of internal bond strength, 48.2 MPa of static bending strength, elasticity modulus 4950
MPa, 1.7 MPa of surface bonding intensity, thickness swelling rate 4.8%, burst size of methanal 2.2mg/100g.
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, it is internal bond strength, quiet
Qu Qiangdu, elasticity modulus and surface bonding intensity are below in embodiment 2 and are produced using bakelite resin nano powder adhesive
Wood-based plate；And thickness swelling rate and burst size of methanal are more than embodiment 2.
Embodiment 3
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.07MPa, the temperature control of adhesive when concentration
At 40 DEG C, it is concentrated into solid content 70%.Concentrate is in -50 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.03mbar, -50 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.003mbar, freeze temperature obtain dry powder at -60 DEG C.It is dry
Powder is ground through nanon ball-mill at 250 DEG C, is ground to screening value 600nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is applied in wood wool, and nano-powder is uniformly mixed with wood wool through mechanical agitation, and wood wool is dried to relative moisture content
40%, the applied amount of nano-powder is calculated with over dry wood shavings quality 15%.Sizing wood shavings enter hot press precompressed, hot press after mating formation
210 DEG C are warming up to, heat preservation.The hot precompressed curve of slab is slowly to boost to unit pressure 3MPa, after pressurize 5min, slowly unloads and is depressed into
Unit pressure 0.3 MPa, pressurize 5min are denoted as breathing 1 time, thorough release after continuously breathing 4 times.Slab immediately enters after release
Another 1 hot press hot pressing, 190 DEG C, hot pressing pressure 2.5MPa, hot pressing time 1.5min/mm of hot pressing temperature.Embodiment result：High humidity
Under the conditions of the carrying shaving board that uses, density 0.65kg/m3, plate thickness 10mm, 1.65 MPa of interior bonding strength, static bending strength
24.2 MPa, 3200 MPa of elasticity modulus, humidity resistance（Interior bonding strength after boiling water boiling）0.54 MPa, water sucting thickness is swollen for 24 hours
Swollen rate 6.5%, burst size of methanal 4.1mg/100g.
Comparative example：Using commercially available phenolic resin adhesive, wood wool relative moisture content is dried to 8%, resin added
Identical as implementation column 3, conventional precompressed mode, hot compression parameters are same as Example 3.Comparative example result：Make under super-humid conditions
Carrying shaving board, density 0.65kg/m3, plate thickness 10mm, 0.71 MPa of interior bonding strength, 20.2 MPa of static bending strength,
2900 MPa of elasticity modulus, humidity resistance（Interior bonding strength after boiling water boiling）0.34 MPa, thickness swelling rate 10.5% for 24 hours,
Burst size of methanal 4.1mg/100g.
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, it is internal bond strength, quiet
Qu Qiangdu, elasticity modulus and humidity resistance（Interior bonding strength after boiling water boiling）It is below in embodiment 3 and uses bakelite resin nano
The wood-based plate that powder adhesive is produced；And thickness swelling rate and burst size of methanal are more than embodiment 3 for 24 hours.
Embodiment 4
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.08MPa, the temperature control of adhesive when concentration
At 50 DEG C, it is concentrated into solid content 80%.Concentrate is in -60 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.04mbar, -55 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.004mbar, freeze temperature obtain dry powder at -55 DEG C.It is dry
Powder is ground through nanon ball-mill at 260 DEG C, is ground to screening value 800nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is applied in wood wool, and nano-powder is uniformly mixed with wood wool through mechanical agitation, and wood wool is practical opposite without drying
The applied amount of moisture content 70%, nano-powder is calculated with over dry wood shavings quality 20%.Sizing wood shavings enter hot press precompressed after mating formation,
Hot press is warming up to 220 DEG C, heat preservation.The hot precompressed curve of slab is slowly to boost to unit pressure 3.5MPa, after pressurize 5min, is delayed
Slow unload is depressed into unit pressure 0.2 MPa, pressurize 5min, is denoted as breathing 1 time, thorough release after continuously breathing 4 times.Slab after release
Immediately enter another 1 hot press hot pressing, 220 DEG C, hot pressing pressure 2.5MPa, hot pressing time 1.5min/mm of hot pressing temperature.Embodiment knot
Fruit：The heavily loaded shaving board used under high humidity state, density 0.65kg/m3, plate thickness 10mm, internal bond strength 1.89 MPa are quiet
34.2 MPa of Qu Qiangdu, 4770 MPa of elasticity modulus, for 24 hours thickness swelling rate 6.4%, internal bond strength（Interior glue after boiling water boiling
Close intensity）0.74 MPa, burst size of methanal 2.5mg/100g.
Comparative example：Using commercially available phenolic resin adhesive, wood wool relative moisture content is dried to 8%, resin added
Identical as implementation column 4, conventional precompressed mode, hot compression parameters are same as Example 4.Comparative example result：Make under high humidity state
Heavily loaded shaving board, density 0.65kg/m3, plate thickness 10mm, 0.89 MPa of internal bond strength, 24.2 MPa of static bending strength,
3770 MPa of elasticity modulus, internal bond strength（Interior bonding strength after boiling water boiling）0.44 MPa, for 24 hours thickness swelling rate
7.4%, burst size of methanal 3.5mg/100g.
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, it is internal bond strength, quiet
Qu Qiangdu, elasticity modulus and internal bond strength（Interior bonding strength after boiling water boiling）It is below in embodiment 4 and is received using phenolic resin
The wood-based plate that rice flour body adhesive is produced；And thickness swelling rate and burst size of methanal are more than embodiment 4 for 24 hours.
Embodiment 5
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.09MPa, the temperature control of adhesive when concentration
At 45 DEG C, it is concentrated into solid content 75%.Concentrate is in -55 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.05mbar, -55 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.005mbar, freeze temperature obtain dry powder at -60 DEG C.It is dry
Powder is ground through nanon ball-mill at 270 DEG C, is ground to screening value 700nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is applied on strip wood shavings, and nano-powder is uniformly mixed with strip wood shavings through mechanical agitation, and strip wood shavings are real without drying
The applied amount of border relative moisture content 80%, nano-powder is calculated with over dry wood shavings quality 18%.After being glued strip wood shavings orienting spreading
Into hot press precompressed, hot press is warming up to 230 DEG C, heat preservation.The hot precompressed curve of slab is slowly to boost to unit pressure
It after 3.0MPa, pressurize 10min, slowly unloads and is depressed into unit pressure 0.1 MPa, pressurize 5min, be denoted as breathing 1 time, continuous breathing 4 times
Thorough release afterwards.Slab immediately enters another 1 hot press hot pressing, 200 DEG C, hot pressing pressure 2.5MPa of hot pressing temperature, hot pressing after release
Time 2.0min/mm.Embodiment result：Load-bearing oriented wood chipboard under dampness, density 0.65kg/m3, plate thickness 8mm,
1.56 MPa of internal bond strength, 52.5 MPa of parallel static bending strength, 37.7 MPa of vertical static bending strength, the parallel modulus of elasticity in static bending
6950 MPa, 4010 MPa of vertical curve elasticity modulus boil parallel 19.6 MPa of static bending strength after 2h, and static bending strength is hung down after boiling 2h
Helicopter-11 .2 MPa, thickness swelling rate 7.8% for 24 hours, burst size of methanal 3.1mg/100g,.
Comparative example：Using commercially available phenolic resin adhesive, strip plane spends moisture content to dry to 8% relatively, is glued
, conventional precompressed mode identical as implementation column 5 is measured, hot compression parameters are same as Example 5.Comparative example result：Under dampness
Load-bearing oriented wood chipboard, density 0.65kg/m3, plate thickness 8mm, 0.56 MPa of internal bond strength, parallel static bending strength 32.5
MPa, 17.7 MPa of vertical static bending strength, 4950 MPa of the parallel modulus of elasticity in static bending, 2010 MPa of vertical curve elasticity modulus are boiled
Static bending strength after 2h（It is parallel）15.6 MPa boil static bending strength after 2h（Vertically）7.2 MPa, for 24 hours thickness swelling rate
10.8%, burst size of methanal 5.1mg/100g.
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, internal bond strength are put down
Row static bending strength, the parallel modulus of elasticity in static bending, vertical curve elasticity modulus, boils static bending strength after 2h at vertical static bending strength（It is flat
Row）With boil static bending strength after 2h（Vertically）It is below the people produced using bakelite resin nano powder adhesive in embodiment 5
Make plate；And thickness swelling rate and burst size of methanal are more than embodiment 5 for 24 hours.
Embodiment 6
Thermosetting property water-soluble phenolic resin adhesive is sticked agent to concentrate at vacuum degree 0.08MPa, the temperature control of adhesive when concentration
At 40 DEG C, it is concentrated into solid content 65%.Concentrate is in -50 DEG C of pre-freezes to complete ice knot；Lyophilization section, vacuum degree
0.06mbar, -50 DEG C of freeze temperature；Parsing-desiccation section, vacuum degree 0.006mbar, freeze temperature obtain dry powder at -70 DEG C.It is dry
Powder is ground through nanon ball-mill at 280 DEG C, is ground to screening value 900nm, is obtained nano-powder.Nano-powder is blown with air-flow to be spread
Mode is uniformly applied on board using poplar board, and for veneer without drying, practical relative moisture content is 90%, the applied amount of nano-powder with
75g/m2It calculates.Enter hot press precompressed after being glued the normal assembly of veneer, hot press is warming up to 250 DEG C, heat preservation.The hot precompressed of slab
Curve is slowly to boost to unit pressure 1.5MPa, after pressurize 6min, slowly unloads and is depressed into unit pressure 0.1 MPa, pressurize 5min,
It is denoted as breathing 1 time, thorough release after continuously breathing 4 times.Slab immediately enters another 1 hot press hot pressing, hot pressing temperature 120 after release
DEG C, hot pressing pressure 1.0MPa, hot pressing time 1.0min/mm.Embodiment result：Plywood for concrete form, plate thickness 15mm, glue
1.99 MPa of intensity, 59.5 MPa of rift grain static bending strength, band static bending strength 47.7MPa, 7250 MPa of modulus of elasticity parellel to grain are closed,
Tangential elastic module 5780 MPa, burst size of methanal 3.5mg/L.
Comparative example：Using commercially available phenolic resin adhesive, veneer relative moisture content is dried to 8%, resin added with
Implementation column 6 is identical, conventional precompressed mode, and hot compression parameters are same as Example 6.Comparative example result：Concrete blinding glue
Plywood, plate thickness 15mm, 0.95 MPa of bonding strength, 49.2 MPa of rift grain static bending strength, 37.5 MPa of band static bending strength, rift grain
6200 MPa of elasticity modulus, tangential elastic module 4700 MPa, burst size of methanal 4.7mg/L.
As can be seen from the comparison result, the wood-based plate produced using phenolic resin adhesive, bonding strength, rift grain
Static bending strength, band static bending strength, modulus of elasticity parellel to grain and tangential elastic module are below in embodiment 6 to be received using phenolic resin
The wood-based plate that rice flour body adhesive is produced；And burst size of methanal is more than embodiment 6.
The present invention is disclosed with preferred embodiment above, so it is not intended to limiting the invention, all to take equivalent replacement
Or the technical solution that the scheme of equivalent transformation is obtained, it all falls in protection scope of the present invention.
Claims (9)
1. a kind of preparation method of thermosetting property water soluble phenol resin nano-powder adhesive, it is characterised in that including following step
Suddenly：
Step 1, thermosetting property water-soluble phenolic resin adhesive stick the vacuum concentration of agent；
Step 2 sticks agent to the thermosetting property water-soluble phenolic resin adhesive after step 1 concentration and carries out vacuum freeze drying；
Step 3 is ground and sieves to sticking agent through vacuum freeze drying treated thermosetting property water-soluble phenolic resin adhesive,
Obtain thermosetting property water soluble phenol resin nano-powder adhesive.
2. the preparation method of thermosetting property water soluble phenol resin nano-powder adhesive according to claim 1, feature
It is：In step 1, the vacuum concentration condition that thermosetting property water-soluble phenolic resin adhesive sticks agent is：Vacuum degree be 0.05 ~
0.09MPa, temperature concentrated in vacuo are 20 ~ 50 DEG C, and the solid content after concentration is 50 ~ 80%.
3. the preparation method of thermosetting property water soluble phenol resin nano-powder adhesive according to claim 1, feature
It is：In step 2, vacuum freeze drying is divided into precooling process, lyophilization process and parsing drying process；Wherein, it is pre-chilled
The temperature of jelly process is less than -40 DEG C, and the vacuum degree of lyophilization process is 0.01 ~ 0.1mbar, freeze temperature is -40 ~ -60
DEG C, the vacuum degree of parsing-desiccation process is 0.001 ~ 0.01mbar, freeze temperature -60 ~ -80 DEG C.
4. the preparation method of thermosetting property water soluble phenol resin nano-powder adhesive according to claim 1, feature
It is：In step 3, grinding uses nanon ball-mill, and grinding temperature is between 190 ~ 280 DEG C；Particle size distribution range exists after screening
Between 400 ~ 900nm.
5. the thermosetting property water soluble phenol resin nano-powder adhesive prepared using the method for any one of claim 1 ~ 4 is in people
Make the application in plate production, it is characterised in that include the following steps：
Step 1 is glued wood-based plate by the way of dry method sizing；
Step 2, artificial board substrate after sizing through mat formation or assembly after carry out the hot precompressed of type of respiration.
6. thermosetting property water soluble phenol resin nano-powder adhesive answering in Wood-based Panel Production according to claim 5
With, it is characterised in that：Be glued object be artificial board substrate in wood shavings layer, fibrous layer or veneer layer, the wood shavings layer, fibrous layer and
The relative moisture content of veneer layer is between 30 ~ 100%.
7. thermosetting property water soluble phenol resin nano-powder adhesive answering in Wood-based Panel Production according to claim 5
With, it is characterised in that：In step 1, bakelite resin nano powder adhesive be applied in such a way that air-flow blows and spreads wood shavings layer or
Fiber layer surface, continuous mechanical agitation, resin added are the 5 ~ 20% of wood shavings layer or fibrous layer over dry weight；Or bakelite resin nano
Powder adhesive is applied to the surface of veneer layer in such a way that air-flow blows and spreads, and resin added is 50 ~ 100g/m2。
8. thermosetting property water soluble phenol resin nano-powder adhesive answering in Wood-based Panel Production according to claim 5
With, it is characterised in that：In step 2, the hot precompressed of type of respiration refers to being kept the temperature after hot press is increased to assigned temperature, by wood-based plate
Slab is placed in hot press and opens after shelves slowly boost to specified unit pressure pressurize for a period of time, slowly unloads and is pressed onto specified unit pressure
Pressurize for a period of time, often undergoes the period of a boosting ~ pressurize ~ release ~ pressurize again afterwards, is denoted as breathing 1 time.
9. the thermosetting property water soluble phenol resin nano-powder adhesive according to claim 5 or 8 is in Wood-based Panel Production
Application, it is characterised in that：In step 2, the unit pressure of the hot precompressed of type of respiration between 0 ~ 5MPa, precompressed temperature 190 ~
Between 250 DEG C, respiration rate is more than 3 times.
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